Varnish, enamel, or lacquer composition.



UNITED STATES PATENT OFFICE- JONAS W. AYLSWORTH, OF EAST ORANGE, NEW JERSEY, ASSIGNOR TO CONDENSITE .COMIPANY OF AMERICA, OF GLEN RIDGE, NEW JERSEY, A CORPORATION OF NEW JERSEY.

VAB NISH, ENAMEL, 0B LACQUER COMPOSITION.

Specification of Letters Patent.

Patented Apr. 2'7, 1915.

Ho Drawing. Original application filed February 11, 1910, Serial No. 543,239. Divided and this application filed December 2, 1913. Serial No. 804,220.

for-use as an enamel, lacquer or varn1sh,.

and my'object is the production of such a composition.

Thisapplication is a division of my Pat ent No. 1,098,608, dated June 2, 1914, entitled enamel lacquer or varnish.- The patcnt referred to claims as a composition of matter or as a varnish ingredient, a. mixture of certain normally-non-liquid substances which are soluble in common solvents, and which are capable of combining together on application of heat to form a hard, infusible insoluble product.

-The present application describes and claims a. varnish or enamel composition and process of making it, the same comprising a solution of 'the mi-gture of non-liquid ingredients; referred toiabove, in a suitable solvent, which-composition hardens on subsequ'ent-heat treatment. 5 My. invention contemplates such a varnish or enamelas may be formed on metals and wood, or is adapted to form ahard surface on cardboard, fabric, paper,-le,ather, 'etc., to form asurface adapted for embossing operations, making negatives, matrices for enravin and rintmg, formin a hard surace suitable or molding soun records, and incorporating with various inert pulverized materials an .jpigments to form veneers for wood. It also is adapted to be incorporated with woven fabrics or paper to form bindings .for books, and in the manufacture of a'vari'ety. of articles.

My invention comprises broadly a; fusible resin of phenolic origin, which -has mixed therewith; substance which is adapted to react'with the resin upon the application of 'sufiicient heat to form. a hard insoluble consozdensa-tion product.

41101 9 specifically, my. invention comprises '1!) whichlis soluble I in the usual solvhntsizofi shellac,- umd "which may; range from pale amber to various shades of trans parent brown in color, and which hardens on the application of heat at a temperature of from 170 to 220 degrees F., or higher. The varnish upon heating, as described, forms a refractory enamel more refractory than ebonite or hard rubber, and almost equaling ivory in hardness and strength. It is at the same time more capable than are the substances mentioned of withstanding the action of chemical agents and heat.

My improved varnish composition is formed by the incorporation of substances containing the methylene radical CH preierably hexa-methylene-amin or hexa-methylene-tetra-amin, as it is somestimes called (CH,),,N with a phenol resin, such as described in my patent 1,102,630 dated July 7, 1914, plastic composition and process of manufacturing the same, and Patent No.

1,029,737, grant'edfJune 18, 1912. or, in place of hexa-methylene-tetra-amin, I may use the product obtained by reactin upon aqueous solutions-of ammoniawith ormaldehyde or polymersthereof, which product may contain other methylene-amins, as explanned in my Patent No. 1,020,593, granted March 19, 1912. Various ofthe so-called shellac substitutes of phenolic o'r cresolic origin may, however, be substituted for the phenol resin referredzto above, with good results, in many of the uses of the enamel.

The resin or shellac substitute and the methylene-amin are dissolved in a suitable solvent such as alcohol, acetone or equivalent solvent. The, :methylene-amin compoundperforms the function of reacting with the fusible phenol condensation product or phenol resinupon the application of su-fficient heat to harden the same by transforming it into an infusible final eondensar tion product, as is described in my Patent ammomais eyolyed. withcomparative 42 .The hexa methylene-amin or? other heat treatment. 1 6

methylene-amin compound seems to be tlie most suitable hardenin substance which can be used, although ot er substances containing the methylene radical, as formalde-. hyde, tri-oxymethylene, etc., may be used.

With the methylene-amin compounds, however, there is never any danger of losing any of the same by evolution as gas, if the composition is 'to remain for some time beforeits application and hardening by heat treatment, since the methylene-amin only gives up its methylene by combination with sucha substance as the phenol resin upon I prefer, as I have stated, to use the articular phenol .resin described in my atents No. 1,102,630 and No. 1,029,737 referred to rather than an. .of the shellac substitutes mentioned, or mixture with .the hardening agent, and for many puroses the mixture with this described resin as particular advantages. My phenol resin, as described in-the' said-application, j is a fusible, soluble, phenol-formaldehyde -25 c-"ndensation product, in which the formaldehyde is all combined with the phenol, and there is no free phenol, oronly a small, as certainable amount; This resin is a final product, in the sense vthat-it can not be transformed into the infusible-irisoluble product by any amount of heating, at any temperature, either .alone' or with basic or acid condensing agents," It --is preferably completely dehydrated b heating to about 400 F. -It ispreferab y the use oi? any I condensing agent. When hexa-methylene-tetra-amin or a solid, anhydrous. polymerized formaldehyde like "tri- 'oxy-methylene is used as" the hardening agent, it should be noted that this ingredient also is anhydrous.

The ingredients may-be eeparately dissolved in the solvent "and "mixed, or they may be dissolved together: 01 the methylene-aminand the phenol resin ma be mixed while the infused condltion at from 200-to 23 0 degrees-=15: without the use of a solvent. This mixture may'then be f-rolled when it has cooled sufiiciently to-become pasty into thinisheets -or laminae suitable for being dissolved-in the-"solvent, or thejmateria-l may bejformed' in thin "sheets -by other means. Thej lastfdescribed' form of the compositionfis' desirable for many uses, as it may be sold and transported in dry state in rolls, the purchaser or 'user dissolving the same in a suitable'solution when he is ready to:.apply thecomposition'in the same manner The comp ion formed; with a methylene=amincompound may be -l'r ept for 'a2cons s s se m and sidei'able time-in solutionin' closed receptacles withouF-harmfd -'change.-: It; is-nonjcor'rosive to metals either in solution or-dry,

formed without and forms an efiicient preservative coating for metals to prevent oxidation and other corrosive actions. I

When the meth lene-amin com ound' is mixed with the p enol resin in tge' fused state, the mixingv and rolling of the material are carried outwithout change of the material into the hard infusible product, since the hardening reaction does not take place immediately, but is. gradual at the temperatureregiired for the mixing of the ingredients. ardening of the film of varnish or enamel after evaporation of the solvent takes place at quite moderate temperatures and is greatly accelerated by increased temperatures. This hardening requires no compensating pressure to prevent rot-hing or the formation of bubbles, and the film is formed without cracks or other defectsdue to the evolution of gas during'the finallreaction of the ingredients. The-varnish or enamel may be hardened by passing-any bod which gives out radiant heat wen'the sur ace of the enamel film closeto the s'ame, but not in contact therewith. Thus, a heated flat iron, electric heater, or similar heat- -ingde vice,-may be used.-

1 Suitable proportions o'f th'e enamel V 500 parts of solvent whic' may be wood alk cohol, methylated spirits, grain 'alcohdi' denatured;- alcohol, acetone, or mixtures the same with each-other or"with smalljpercentages of water.

1 when the liquid (in-Ame or; Mas-s; de-

jrotective coating on signed to be used as a p metal, the proportion o the he remethylaneamin' maybe reduced from 41:06 parts to parts of'the phenol resin."-=- Whenthe liquid enamel or la nor is deslgned tWbe used as-a film applie to a. suitable h i g to be'emboss'ed or shaped after evaporation of the solvent and hardening byheat, a solid solvent ingredientfsuchis' those men'- 'tioned in Patent' 1No."-'-'1 1 02 ,630'=or- Patent Not- 15020598aboveftefeirred to, may'ibe added in;Percentages' WhicHmay be varied between-'5 and 25 per cefia', d endent upon the particular use desired, the natui'eof the solid solvent 'and itssolubll ty solvent used in' the; l'a'c'que'r. a

in the volatile I a The solid solvefits' mentioned arm No. 1,102,630 as there-described are; final'product'solvents" by which term:g1-e

included only such Weill solve thefultn'nate condensation product or combine thereafith' at the baking tempera- ;'ture; f-rerider' it plasticat jsuch temperature, "and rmain fas'a arfi of the product mthe condition ofsioli' solutiong bothwhen the ultimate product is hot and-when it; is-cold.

Among theezgampls oi this: which ma be -mentioned are naphthalene and some of its" derivatives,- 'such ms' mtro and" chloroderivatives,- especiall the mono-nitro and di-nitro and mono-c loro and tetra-chloro napthalenes, di-nitro benzene, preferably the meta variety, acetanilid, ricinoleic acid and ricinelaidic acid and their anhydrids, benzoic acid and anhydrid'and di-phenylamim' My Patent No. 1,065,495, granted June 24, 1913, covers in its broader aspects a composition similar to that described and claimed herein. The said patent is however, limited in its claim to the use of a normally nonvolatile fiuid solvent, or to a solvent comprising an organic liquid which is immiscible with water and whose boiling point exceeds that of water, or specifically to liquid mono-chloro-naphthalene, or to a solvent containing both a volatile solvent and a normally non-volatile liquid solvent, or organic liquid non-water-miscible solvent of boiling point exceeding that of water.

The present application claims a varnlsh or enamel comprising substances, such as phenol resin and a hardening agent therefor, dissolved in a volatile solvent. It also claims a varnish or enamel comprising substances capable of transformation by chemical reaction upon application of heat, a volatile solvent therefor, or, generically expressed, a solvent therefor comprising a liquid oxyg'en compound of the aliphatic series, and an additional organic element, soluble in said solvent, referred to as an aromatic compound, or a compound of the benzene series, or as a specific example, dinitro-benzene. It is to be noted that the body so described is not limited to a normally fluid or liquid substance as is the case with the non-volatile or non-water-miscible organic solvent included in the claims of my Patent No. 1,065,495, referred to above.

All of the so-called solid solvents or final product solvents referred to above as desirable to be added to the liquid enamel in certain circumstances, are aromatic compounds, and various of them, such for example as di-nitro-benzene, benzoic acid, acetanilid, etc., are compounds of the benzene series. Such bodies dissolve, in the proportions used, in the acetone, alcohol, or equivalent solvent used for the varnish or enamel, and produce the-desirable properties referred to above.

Having now described my invention what I claim and desire to protect by Letters Patent is 1. As a new composition of matter, a varnish or enamel comprising a volatile solvent, and a fusible resin of phenolic origin and hexa-methylene-tetra-amin, both dissolved in said solvent, substantially as described. T

2. As a new composition of matter, a varnish or enamel comprising a volatile solvent, and a fusible resin of phenolic origin and a substance which is capable of combining with the said resin on application of heat to harden the same to infusibility and insolubility, both dissolved in said solvent, the said resin being character zed by its incapability of transformation into an infusible and insoluble body, when not mixed with such a substance, substantially as described.

3. As a new composition of matter, a varnish or enamel comprising a volatile solvent, and an anhydrous phenol resin and an anhydrous methylene-containing hardening agent therefor, both dissolved in said solvent, substantially as described.

4. As a new composition of matter, a varnish or enamel comprising a volatile solvent, and an anhydrous phenol resin and an anhydrous methylene-containing hardening agent therefor, both dissolved in said solvent, the said resin bein characterized by its incapability of trans ormation into an infusible and insoluble body, when not mixed with such an agent, substantially as described.

5. As a new composition of matter, a varnish or enamel comprisin a volatile solvent, a phenol resin substantlally free from uncombined formaldehyde or equivalent, and hexa-methylene-tetra-amin, in the proportion of from 4 to 10 per cent. of the weight of the resin, both said resin and hexamethylene-tetra-amin being dissolved in said solvent, substantially as described.

6. As a new composition of matter, a varnish or enamel comprising substances capable of transformation by chemical reaction upon application of suflicient heat to form a hard infusible phenolic condensation product, a volatile solvent comprising a liquid oxygen-compound of the aliphatic series, and a compound of the benzene series soluble in said volatile solvent, substantially as described.

7. As a new composition of matter, a varnish or enamel comprising substances capable of transformation by chemical reaction upon application of sufficient heat to form a hard infusible phenolic condensation product, a solvent therefor comprising a liquid oxygen-compound of the aliphatic series, and a compound containing the benzene ring soluble in said solvent, substantially as described.

8. As a new composition of matter, a varnish or enamel comprising substances capable of transformation by chemical reacproduct, a solvent therefor comprising a liquiioxygen-coinpoiind of the ali hatic liquid oxygen-compound of the aliphatic .series, and acyclic-'Thydrocarbon, su stanseries, and di-nitro benzene, substantially as tially as described r 1 I described. This specification signedand witnessed 5 1 0. fis a new lcomposition oi matter,'a 1 this 28th day of November; 1913.

varnis or ename comprisin su stances capable of transformation by chemical reac- JONAS -S tion upon application of suflicent heat to Witnesses: form a hard lnfusible phenolic condensation FREDERICK BAGHMANN, 10 product, a solvent therefor comprising a HENRY LANAHANF 

